CN104787852A - Preparation method of inertial substrate nanosilver-ferroalloy electrode, obtained electrode and application of electrode - Google Patents
Preparation method of inertial substrate nanosilver-ferroalloy electrode, obtained electrode and application of electrode Download PDFInfo
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Abstract
The invention relates to a preparation method of an inertial substrate nanosilver-ferroalloy electrode, the obtained electrode and application of the electrode. The method comprises the following steps: cleaning an inertial substrate; pre-inoculating nano-ferrum; inoculating a nanosilver-ferroalloy; cleaning; storing. The electrode prepared by the method can be used for removing harmful oxygen bearing negative ions in water, and the removal efficiency is high and no secondary pollution exists; by controlling the deposition conditions of nanosilver and nano-ferrum, the structure and the grain of the nanosilver-ferroalloy can be effectively controlled, and the grain size ranges from 50 nm to 350 nm. The whole preparation method can be carried out in a normal temperature condition, is mild in reaction condition, simple in preparation process and easy to realize, and has no special requirements on the external environmental condition.
Description
Technical field
The present invention relates to the preparation method of a kind of inert substrate nanometer silver-iron electrode, the electrode obtained and application thereof, belong to water treatment catalysis electrode technical field.
Background technology
According to the knowledge of the applicant, in recent years along with industry and agriculture developing rapidly, in global water body, the concentration of oxo-anions (as nitrate, bromate, arsenate etc.) is increase trend.These harmful oxo-anions in water body can cause serious harm to human body, and the content therefore controlling contained harmful oxo-anions in water body seems particularly important.
At present, existing a variety of methods control the content of oxo-anions in water body, as ion-exchange, and reverse osmosis, chemical reduction etc.Wherein, electrochemical process causes the extensive concern of people due to its advantage such as green, efficient.
Ferro element is rich reserves in the earth's crust, and nano zero valence iron has comparatively strong reducing property, has been widely used in the removal of water body objectionable impurities.But Zero-valent Iron is easy passivation inactivation in atmosphere, therefore needs to do further modification to it.In addition, nanometer silver, because of its good catalytic activity and stability, is with a wide range of applications at alloy modification electrode field.
Applicant thinks after deliberation, if effectively can utilize the advantage of above-mentioned two kinds of catalytic materials and prepare corresponding Nanoalloy electrode, should be able to improve the catalytic performance of electrode by synergy.But there is the shortcoming such as apparatus expensive, complicated operation in alloy preparation method conventional at present, is unfavorable for applying.Need the method developed and can prepare above-mentioned Nanoalloy electrode simply and easily badly.
Summary of the invention
Technical problem to be solved by this invention is: overcome prior art Problems existing, provides the preparation method of a kind of inert substrate nanometer silver-iron electrode, and process is simple, is easy to realize, and the electrode obtained effectively can remove harmful oxo-anions in water.The present invention also provides the electrode obtained by this preparation method, and the application of this electrode.
The technical scheme that the present invention solves its technical problem is as follows:
A preparation method for inert substrate nanometer silver-iron electrode, is characterized in that, comprise the following steps:
The first step, inert substrate is put ultrasonic cleaning first scheduled time in ultrapure water; Then inert substrate is put in dehydrated alcohol ultrasonic cleaning second scheduled time; Afterwards inert substrate is put in ultrapure water ultrasonic cleaning the 3rd scheduled time; Inert substrate is dried up with nitrogen; 3rd the scheduled time >=first the scheduled time >=0.5 hour, and the 3rd the scheduled time >=second the scheduled time >=0.5 hour;
Second step, under nitrogen protection, by the first complete submergence at least 0.5 hour in iron ion mixing solutions of the first step gained inert substrate, more complete submergence at least 0.2 hour in sodium borohydride solution; So repeatedly after 3-20 time, with ultrapure water inert substrate, obtain the inert substrate of pre-vaccination Nanoscale Iron;
3rd step, with second step gained inert substrate for working electrode, be to electrode with platinum plate electrode, and adopt reference electrode; By working electrode, be immersed in silver ions mixing solutions completely to electrode and reference electrode, form three-electrode electro Chemical electrolyzer system; Afterwards, apply the constant potential that potential value is-2.0V to-0.05V on the working electrode (s, application time is 5-600 second, makes nano silver particles be deposited on Nanoscale Iron surface, obtains the inert substrate of inoculation nanometer silver-iron alloy;
4th step, the 3rd step gained inert substrate to be cleaned with deoxygenation ultrapure water, dehydrated alcohol, deoxygenation ultrapure water successively, obtain inert substrate nanometer silver-iron electrode finished product.
The technical scheme that the inventive method is perfect is further as follows:
Preferably, in the first step, first scheduled time was 0.5-2 hour, and second scheduled time was 0.5-2 hour, and the 3rd scheduled time was 1-2 hour; In second step, submergence 0.5-1.5 hour in iron ion mixing solutions, submergence 0.2-1 hour in sodium borohydride solution, ultrapure water 3-5 time; In 4th step, the detailed process of cleaning is: by inert substrate first with deoxygenation ultrapure water cleaning 2-5 time, then with washes of absolute alcohol 3-4 time, finally cleans 3-5 time with deoxygenation ultrapure water.
Preferably, also comprise: the 5th step, to be immersed in completely in dehydrated alcohol by the 4th step gained inert substrate nanometer silver-iron electrode finished product, in the environment of-20 DEG C to 0 DEG C, sealing is preserved.
Preferably, described inert substrate is one of vitreous carbon fibers, conductive glass, graphite, gac.
Preferably, in second step, described iron ion mixing solutions is made up of ferrous salt, sodium sulfate, buffer reagent and water, and described ferrous salt is one of ferrous sulfate, iron protochloride, ferrous ammonium sulphate, and described buffer reagent is xitix, one of citric acid and polyvinylpyrrolidone; The molar concentration rate of described ferrous salt and sodium sulfate is 1:25-600, and the ratio of described buffer molarities and ferrous salt and sodium sulfate volumetric molar concentration sum is 1:10-3000.
More preferably, described ferrous salt is ferrous sulfate, and the pH value of described iron ion mixing solutions is 2.5-3.5.
Preferably, in the 3rd step, described silver ions mixing solutions is made up of Silver Nitrate, SODIUMNITRATE and water, and the molar concentration rate of described Silver Nitrate and SODIUMNITRATE is 1:5-300.
Preferably, in the 3rd step, described reference electrode is one of saturated calomel electrode, mercury-mercuric oxide electrode, silver chloride electrode, reversible hydrogen electrode.
The present invention also provides: the electrode obtained by above-mentioned preparation method.
The present invention also provides: above-mentioned electrode is for removing the purposes of harmful oxo-anions in water.
Inert substrate nanometer silver-iron electrode prepared by the present invention, can be used for removing harmful oxo-anions in water, removal efficiency is high, non-secondary pollution; By controlling the mode of deposition of Nanoscale Iron and nanometer silver, effectively can control structure and the particle diameter of nanometer silver-iron alloy, size scope is 50-350nm; Whole preparation method can carry out under normal temperature condition, and reaction conditions is gentle, and preparation process is simple, and be easy to realize, envrionment conditions is without particular requirement to external world.
Accompanying drawing explanation
Fig. 1 is the SEM figure that the embodiment of the present invention 1 obtains inert substrate nanometer silver-iron electrode.
Fig. 2 is the SEM figure that the embodiment of the present invention 2 obtains inert substrate nanometer silver-iron electrode.
Fig. 3 is the SEM figure that the embodiment of the present invention 3 obtains inert substrate nanometer silver-iron electrode.
Fig. 4 is the catalytic activity phenogram that each electrode of the embodiment of the present invention 4 removes nitrate radical.
Fig. 5 is the catalytic activity phenogram that each electrode of the embodiment of the present invention 5 removes bromate.
Embodiment
With reference to the accompanying drawings and the present invention is described in further detail in conjunction with the embodiments.But the invention is not restricted to given example.
Inert substrate nanometer silver-iron electrode preparation method that the present invention specifically implements, comprising:
The first step, inert substrate is put in ultrapure water ultrasonic cleaning first scheduled time (preferred 0.5-2 hour); Then inert substrate is put in dehydrated alcohol ultrasonic cleaning second scheduled time (preferred 0.5-2 hour); Afterwards inert substrate is put ultrasonic cleaning the 3rd scheduled time (preferred 1-2 hour) in ultrapure water; Inert substrate is dried up with nitrogen; 3rd the scheduled time >=first scheduled time, and the 3rd the scheduled time >=second scheduled time; Inert substrate is one of vitreous carbon fibers, conductive glass, graphite, gac.
Second step, under nitrogen protection, by the first complete submergence at least 0.5 hour (preferred 0.5-1.5 hour) in iron ion mixing solutions of the first step gained inert substrate, more complete submergence at least 0.2 hour (preferred 0.2-1 hour) in sodium borohydride solution; So repeatedly after 3-20 time, with ultrapure water inert substrate (preferably flushing 3-5 time), obtain the inert substrate of pre-vaccination Nanoscale Iron.
Wherein, iron ion mixing solutions is made up of ferrous salt, sodium sulfate, buffer reagent and water, and ferrous salt is one of ferrous sulfate, iron protochloride, ferrous ammonium sulphate, and buffer reagent is xitix, one of citric acid and polyvinylpyrrolidone; The molar concentration rate of ferrous salt and sodium sulfate is 1:25-600, and the ratio of buffer molarities and ferrous salt and sodium sulfate volumetric molar concentration sum is 1:10-3000.Preferably, ferrous salt is ferrous sulfate, and the pH value of iron ion mixing solutions is 2.5-3.5.
3rd step, with second step gained inert substrate for working electrode, be to electrode with platinum plate electrode, and adopt reference electrode; By working electrode, be immersed in silver ions mixing solutions completely to electrode and reference electrode, form three-electrode electro Chemical electrolyzer system; Afterwards, apply the constant potential that potential value is-2.0V to-0.05V on the working electrode (s, application time is 5-600 second, makes nano silver particles be deposited on Nanoscale Iron surface, obtains the inert substrate of inoculation nanometer silver-iron alloy.
Wherein, silver ions mixing solutions is made up of Silver Nitrate, SODIUMNITRATE and water, and the molar concentration rate of Silver Nitrate and SODIUMNITRATE is 1:5-300; Reference electrode is one of saturated calomel electrode, mercury-mercuric oxide electrode, silver chloride electrode, reversible hydrogen electrode.
4th step, the 3rd step gained inert substrate to be cleaned with deoxygenation ultrapure water, dehydrated alcohol, deoxygenation ultrapure water successively, obtain inert substrate nanometer silver-iron electrode finished product.Wherein, the detailed process of cleaning is: by inert substrate first with deoxygenation ultrapure water cleaning 2-5 time, then with washes of absolute alcohol 3-4 time, finally cleans 3-5 time with deoxygenation ultrapure water.
5th step, be immersed in completely in dehydrated alcohol by the 4th step gained inert substrate nanometer silver-iron electrode finished product, in the environment of-20 DEG C to 0 DEG C, sealing is preserved.
Above-mentioned preparation method's the electrode obtained can be used for removing the purposes of harmful oxo-anions in water.
Embodiment 1
The present embodiment preparation method adopts above-mentioned concrete enforcement preparation method, and design parameter is as follows:
In the first step, first scheduled time was 0.5h; Second scheduled time was 0.5h; 3rd scheduled time was 1h.
In second step, complete submergence 0.5h in iron ion mixing solutions, complete submergence 0.2h in sodium borohydride solution; Repeatedly after 3 times, ultrapure water 3 times;
Wherein, in iron ion mixing solutions, buffer reagent is xitix; The molar concentration rate of ferrous salt and sodium sulfate is 1:25, and the ratio of buffer molarities and ferrous salt and sodium sulfate volumetric molar concentration sum is 1:15.
In 3rd step, applying potential value is on the working electrode (s the constant potential of-0.5V, and application time is 120 seconds.
In 4th step, the detailed process of cleaning is: inert substrate is first cleaned 2 times with deoxygenation ultrapure water, then with washes of absolute alcohol 3 times, finally cleans 3 times with deoxygenation ultrapure water.
In 5th step, in the environment of-5 DEG C, sealing is preserved.
As shown in Figure 1, the nanometer silver-iron alloy on its surface of the present embodiment the electrode obtained is cube like structure substantially, and the median size of this nanometer silver-iron alloy is 120nm.
Embodiment 2
The present embodiment preparation method is substantially the same manner as Example 1, and different design parameters is as follows:
In the first step, first scheduled time was 1h; Second scheduled time was 1h; 3rd scheduled time was 1.5h.
In second step, complete submergence 1h in iron ion mixing solutions, complete submergence 0.5h in sodium borohydride solution; Repeatedly after 10 times, ultrapure water 4 times;
Wherein, in iron ion mixing solutions, buffer reagent is citric acid, and the molar concentration rate of ferrous salt and sodium sulfate is 1:200, and the ratio of buffer molarities and ferrous salt and sodium sulfate volumetric molar concentration sum is 1:200.Ferrous salt is ferrous sulfate, and the pH value of iron ion mixing solutions is 2.5-3.5.
In 3rd step, applying potential value is on the working electrode (s the constant potential of-1.2V, and application time is 350 seconds.
In 4th step, the detailed process of cleaning is: inert substrate is first cleaned 3 times with deoxygenation ultrapure water, then with washes of absolute alcohol 3 times, finally cleans 4 times with deoxygenation ultrapure water.
In 5th step, in the environment of-10 DEG C, sealing is preserved.
As shown in Figure 2, the nanometer silver-iron alloy on its surface of the present embodiment the electrode obtained is flower-like structure, and the median size of its nano zero valence iron is 220nm.
Embodiment 3
The present embodiment preparation method is substantially the same manner as Example 1, and different design parameters is as follows:
In the first step, first scheduled time was 2h; Second scheduled time was 2h; 3rd scheduled time was 2h.
In second step, complete submergence 1.5h in iron ion mixing solutions, complete submergence 1h in sodium borohydride solution; Repeatedly after 20 times, ultrapure water 5 times;
Wherein, in iron ion mixing solutions, buffer reagent is citric acid, and the molar concentration rate of ferrous salt and sodium sulfate is 1:500, and the ratio of buffer molarities and ferrous salt and sodium sulfate volumetric molar concentration sum is 1:2000.
In 3rd step, applying potential value is on the working electrode (s the constant potential of-2.0V, and application time is 600 seconds.
In 4th step, the detailed process of cleaning is: inert substrate is first cleaned 5 times with deoxygenation ultrapure water, then with washes of absolute alcohol 4 times, finally cleans 5 times with deoxygenation ultrapure water.
In 5th step, in the environment of-10 DEG C, sealing is preserved.
As shown in Figure 3, the nanometer silver-iron alloy on its surface of the present embodiment the electrode obtained is flower-like structure, and the median size of its nano zero valence iron is 280nm.
Embodiment 4
The present embodiment preparation method is substantially the same manner as Example 1, and different design parameters is as follows:
In second step, complete submergence 0.5h in iron ion mixing solutions, complete submergence 0.2h in sodium borohydride solution; Repeatedly after 3 times, ultrapure water 3 times;
Wherein, in iron ion mixing solutions, buffer reagent is polyvinylpyrrolidone, and the molar concentration rate of ferrous salt and sodium sulfate is 1:300, and the ratio of buffer molarities and ferrous salt and sodium sulfate volumetric molar concentration sum is 1:1000.
In 3rd step, applying potential value is on the working electrode (s the constant potential of-0.8V, and application time is 180 seconds.
As shown in Figure 4, remove for water body nitrate radical, the per surface catalytic activity of the present embodiment the electrode obtained is obviously better than electrode prepared by traditional potentiostatic method and galvanostatic method.In Fig. 4, X-coordinate is working electrode potential E/V (SCE, using saturated calomel electrode as reference electrode), and ordinate zou is current density I/mAcm
-2, strength of solution during measurement is 0.1mol/l sodium hydroxide and 0.05mol/l SODIUMNITRATE.In Fig. 4, A line represents the obtained electrode of constant potential synthesis method, and B line represents the obtained electrode of continuous current synthesis method, and C line represents the present embodiment and obtains electrode, D line represents pure vitreous carbon fibers substrate, and above-mentioned three kinds of electrodes are all inert substrate, substrate surface depositing silver-iron alloy with vitreous carbon fibers.
Embodiment 5
The present embodiment preparation method is substantially the same manner as Example 1, and different design parameters is as follows:
In second step, complete submergence 2h in iron ion mixing solutions, complete submergence 1h in sodium borohydride solution; Repeatedly after 15 times, ultrapure water 4 times;
Wherein, in iron ion mixing solutions, buffer reagent is citric acid, and the molar concentration rate of ferrous salt and sodium sulfate is 1:220, and the ratio of buffer molarities and ferrous salt and sodium sulfate volumetric molar concentration sum is 1:220.
In 3rd step, applying potential value is on the working electrode (s the constant potential of-1.2V, and application time is 350 seconds.
As shown in Figure 5, remove for water body bromate, the per surface catalytic activity of the present embodiment the electrode obtained is obviously better than electrode prepared by traditional potentiostatic method and galvanostatic method.In Fig. 5, X-coordinate is working electrode potential E/V (SCE, using saturated calomel electrode as reference electrode), and ordinate zou is current density I/mAcm
-2, strength of solution during measurement is 0.2mol/l potassium hydroxide and 0.05mol/l potassium bromate.In Fig. 5, A line represents the present embodiment and obtains electrode, and B line represents the obtained electrode of constant potential synthesis method, and C line represents the obtained electrode of continuous current synthesis method, and above-mentioned three kinds of electrodes are all inert substrate, substrate surface depositing silver-iron alloy with vitreous carbon fibers.
In addition to the implementation, the present invention can also have other embodiments.All employings are equal to the technical scheme of replacement or equivalent transformation formation, all drop on the protection domain of application claims.
Claims (10)
1. a preparation method for inert substrate nanometer silver-iron electrode, is characterized in that, comprise the following steps:
The first step, inert substrate is put ultrasonic cleaning first scheduled time in ultrapure water; Then inert substrate is put in dehydrated alcohol ultrasonic cleaning second scheduled time; Afterwards inert substrate is put in ultrapure water ultrasonic cleaning the 3rd scheduled time; Inert substrate is dried up with nitrogen; 3rd the scheduled time >=first the scheduled time >=0.5 hour, and the 3rd the scheduled time >=second the scheduled time >=0.5 hour;
Second step, under nitrogen protection, by the first complete submergence at least 0.5 hour in iron ion mixing solutions of the first step gained inert substrate, more complete submergence at least 0.2 hour in sodium borohydride solution; So repeatedly after 3-20 time, with ultrapure water inert substrate, obtain the inert substrate of pre-vaccination Nanoscale Iron;
3rd step, with second step gained inert substrate for working electrode, be to electrode with platinum plate electrode, and adopt reference electrode; By working electrode, be immersed in silver ions mixing solutions completely to electrode and reference electrode, form three-electrode electro Chemical electrolyzer system; Afterwards, apply the constant potential that potential value is-2.0V to-0.05V on the working electrode (s, application time is 5-600 second, makes nano silver particles be deposited on Nanoscale Iron surface, obtains the inert substrate of inoculation nanometer silver-iron alloy;
4th step, the 3rd step gained inert substrate to be cleaned with deoxygenation ultrapure water, dehydrated alcohol, deoxygenation ultrapure water successively, obtain inert substrate nanometer silver-iron electrode finished product.
2. the preparation method of inert substrate nanometer silver-iron electrode according to claim 1, it is characterized in that, in the first step, first scheduled time was 0.5-2 hour, and second scheduled time was 0.5-2 hour, and the 3rd scheduled time was 1-2 hour; In second step, submergence 0.5-1.5 hour in iron ion mixing solutions, submergence 0.2-1 hour in sodium borohydride solution, ultrapure water 3-5 time; In 4th step, the detailed process of cleaning is: by inert substrate first with deoxygenation ultrapure water cleaning 2-5 time, then with washes of absolute alcohol 3-4 time, finally cleans 3-5 time with deoxygenation ultrapure water.
3. the preparation method of inert substrate nanometer silver-iron electrode according to claim 1, it is characterized in that, also comprise: the 5th step, to be immersed in completely in dehydrated alcohol by the 4th step gained inert substrate nanometer silver-iron electrode finished product, in the environment of-20 DEG C to 0 DEG C, sealing is preserved.
4. the preparation method of inert substrate nanometer silver-iron electrode according to claim 1 or 2 or 3, it is characterized in that, described inert substrate is one of vitreous carbon fibers, conductive glass, graphite, gac.
5. the preparation method of inert substrate nanometer silver-iron electrode according to claim 1 or 2 or 3, it is characterized in that, in second step, described iron ion mixing solutions is made up of ferrous salt, sodium sulfate, buffer reagent and water, described ferrous salt is one of ferrous sulfate, iron protochloride, ferrous ammonium sulphate, and described buffer reagent is xitix, one of citric acid and polyvinylpyrrolidone; The molar concentration rate of described ferrous salt and sodium sulfate is 1:25-600, and the ratio of described buffer molarities and ferrous salt and sodium sulfate volumetric molar concentration sum is 1:10-3000.
6. the preparation method of inert substrate nanometer silver-iron electrode according to claim 5, it is characterized in that, described ferrous salt is ferrous sulfate, and the pH value of described iron ion mixing solutions is 2.5-3.5.
7. the preparation method of inert substrate nanometer silver-iron electrode according to claim 1 or 2 or 3, it is characterized in that, in 3rd step, described silver ions mixing solutions is made up of Silver Nitrate, SODIUMNITRATE and water, and the molar concentration rate of described Silver Nitrate and SODIUMNITRATE is 1:5-300.
8. the preparation method of inert substrate nanometer silver-iron electrode according to claim 1 or 2 or 3, it is characterized in that, in the 3rd step, described reference electrode is one of saturated calomel electrode, mercury-mercuric oxide electrode, silver chloride electrode, reversible hydrogen electrode.
9. the electrode adopting the preparation method of inert substrate nanometer silver-iron electrode described in any one of claim 1 to 8 to obtain.
10. electrode described in claim 9 is for removing the purposes of harmful oxo-anions in water.
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| CN108017119A (en) * | 2017-11-21 | 2018-05-11 | 齐鲁工业大学 | A kind of composite cathode and preparation method thereof |
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| CN1595683A (en) * | 2003-09-10 | 2005-03-16 | 中国科学院物理研究所 | Nanometer metal or alloy composite material and preparation and usage thereof |
| CN102174702A (en) * | 2011-01-11 | 2011-09-07 | 湖南大学 | Preparation method for metallic nano-particle and graphene composite |
| CN102201459A (en) * | 2011-03-30 | 2011-09-28 | 山东大学 | Photoelectrode material of nanometer porous metal load semiconductor and preparation method thereof |
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| CN1595683A (en) * | 2003-09-10 | 2005-03-16 | 中国科学院物理研究所 | Nanometer metal or alloy composite material and preparation and usage thereof |
| CN102174702A (en) * | 2011-01-11 | 2011-09-07 | 湖南大学 | Preparation method for metallic nano-particle and graphene composite |
| CN102201459A (en) * | 2011-03-30 | 2011-09-28 | 山东大学 | Photoelectrode material of nanometer porous metal load semiconductor and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108017119A (en) * | 2017-11-21 | 2018-05-11 | 齐鲁工业大学 | A kind of composite cathode and preparation method thereof |
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